珊瑚状Ni2P修饰新型四足状Cd0.9Zn0.1SZB/WZ同质结光催化剂的高效可见光光催化产氢

随着社会发展,传统化石能源消耗加剧,人类迫切需要开发新型的清洁能源.半导体光催化分解水产氢是一种非常具有潜力解决能源危机的清洁技术.目前,金属硫化物半导体有着合适的能带结构和高效的光催化产氢能力而得到了广泛的研究.通常,为了提高光催化剂产氢性能,添加贵金属助催化剂是一个行之有效的方法.但是贵金属昂贵的价格限制了其大规模的应用,因此有必要研究储量丰富,价格低廉的高效助催化剂.Ni₂P,CoP,Co₂P,MoP,Cu₃P等过渡金属磷化物具有价格低廉,优异的稳定性和催化性能而被用作电催化产氢的催化剂.通常,用于电催化产氢的催化剂往往可以作为光催化产氢的助催化剂.众所周知,催化性能与材料的形貌密切相关,因此,具有棒状、中空、片状等形貌的金属硫化物被制备并用于光催化产氢.然而,四足状结构的金属硫化物研究较少.在已有的Ni₂P(NP)相关研究中,仅合成了纳米颗粒状的NP.本文成功合成了四足状Cd_0.9Zn_0.1S(CZS)和珊瑚状形貌的NP,进一步得到一系列Ni₂P-Cd_0.9Zn_0.1S(NPCZS)光催化剂,采用XRD,SEM,TEM,XPS和ICP-AES测试了样品的结构、形貌、表面成分和元素含量,并测试了样品的光催化产氢性能.采用水热法合成的CZS样品具有特殊的四足状形貌,足部由纳米棒组成.XRD结果表明,四足状CZS中立方相(WZ)和六方相(ZB)共存.经TEM进一步分析,发现CZS中心部位呈ZB相结构,而足部却是WZ相.经光催化性能测试,这种新型四足状CZS表现出优异的光催化产氢性能.进一步通过超声或研磨破坏四足状结构后,发现CZS的产氢性能显著下降,说明四足状形貌是材料性能提高的关键.通过分析WZ和ZB两物相的价带顶和导带底的电位发现,ZB/WZ间形成的同质结可以加速光生载流子的分离和传输.NP也采用水热法制备,其具有珊瑚状形貌.该形貌具有高的比表面积,可以提供更多的活性位点,进一步提高了材料的光催化性能.光催化性能测试表明,NP负载量为12 wt%的NPCZS-12样品表现出很好的产氢性能(l.88 mmol h^-1),是纯CZS的1.43倍.同时,NPCZS-12具有良好的光稳定性和循环使用性能.结合光催化实验、光谱实验、表面光电压和电化学测试的结果发现,四足状形貌、同质结和NP助催化剂的协同效应是NPCZS具有良好光催化性能的主要原因.     

Fabrication and characteristics of self‐aggregation nanoparticles used for conformance control treatment

In order to alleviate the contradiction between injectability of the profile control agent and its profile control performance, a novel core‐shell heterogeneous structure colloidal particles (CSA) were synthesized, and the mechanism of self‐aggregation plugging was proposed. Cross‐linking inside the nanoparticles and chain‐growth polymerization via capturing acrylamide in the aqueous phase result in the formation of core‐shell heterogeneous structures as proved by TEM observation and XPS analysis. Moreover, CSA nanoparticles exhibit good hydrophilic properties, outstanding thermal stability and limited expansion capacity. Effects of different metal cations and surface group on the self‐aggregation time of CSA nanoparticles were systematically studied. Results showed that divalent cations contributed to more significant aggregation of CSA nanoparticles in comparison to monovalent cations. The increasing cations concentration and valency decreased the thickness of electric double layer, which lead to a decrease in the zeta potential. Core flooding test shows that the injection of nanoparticles which diameter is much smaller that of pore‐throats into the target reservoir can not only successfully enter the depth of porous media, but also effectively block the high permeability areas by the formation of self‐aggregation particle clusters. This study provides a new method for the equilibrium between nanoparticles injectivity and in‐depth profile control of nanoparticles.     

Solvothermal Synthesis of Multiple Dihydropyrimidinones at a Time as Inhibitors of Eg5

Solvothermal synthesis of multiple dihydropyrimidinones at a time has been developed in inexpensive and green bio-based solvent lactic acid without any additional catalysts or additives. By this method, thirty new dihydropyrimidinone derivatives were synthesized in two batches and characterized. All of the compounds were screened by Eg5 motor protein ATPase assay, and the positive compounds were tested against the Caco-2 cell line, HeLa cell line, L929 cell line and T24 cell line in vitro. Among them, compound C9 exhibited the best inhibitory activity against motor protein ATPase with an IC₅₀ value of 30.25 μM and significant cytotoxic activity in the micromolar range against the cells above. The Lineweaver–Burk plot revealed that compound C9 was a mixed-type Eg5 inhibitor. A molecular modeling study using the Discovery Studio program was performed, where compound C9 exhibited good binding interaction with Eg5 motor protein ATPase, and this was consistent with the attained experimental results.     

Ultrafast synthesis of near-infrared-emitting aqueous CdTe/CdS quantum dots with high fluorescence

The traditional aqueous route to synthesis CdTe/CdS Core/shell (c/s) quantum dots (QDs) via decomposition of Cd-thiol complexes is usually time consuming. Herein, an ultrafast and facile aqueous synthetic approach under atmospheric pressure for CdTe/CdS c/s QDs with emission from the green to the near-infrared window (535–820 nm) is reported. With purified CdTe core QDs diluted in solution of Cd-3-mercaptopropionic acid (MPA) complexes, CdTe/CdS c/s QDs with emission wavelengths at 700 and 800 nm can be obtained within 20- and 45-min refluxing under the optimized experimental conditions, respectively. This is the most rapid way to prepare CdTe/CdS c/s QDs in aqueous phase, and the obtained QDs were highly luminescent without postsynthesis treatment. The influences of various experimental factors, including Cd²⁺ concentration, MPA-to-Cd ratio, pH value, and dilution ratio on the growth rate and luminescent properties of the obtained CdTe/CdS c/s QDs, have been taken into consideration. The three processes “purification-dilution-addition” ensure the synthesis environment with high pH value and low core concentration and have a marked impact on the rapid synthesis rate and the resulting high fluorescence of CdTe/CdS c/s QDs.     

Preparation and properties of ZnMoO4 anode materials with polymer network gel method

Polymer network gel method combines the advantages of solid-phase method and liquid phase method, triggering acrylamide (AM) radical polymerization in aqueous solution and N, N′- methylene bis acrylamide (MBAM) active double bond cross-linking reaction, forming polymer chains to form a three-dimensional network. The polymer network space formed by the gel is bound and evenly distributed to the ions in the solution, thereby reducing the contact and aggregation of molecules and achieving the purpose of uniform particle size and small particle size. The principle diagram of network gel is shown in Figure. Using cubic zinc acetate and ammonium molybdate tetrahydrate as raw materials, cubic ZnMoO₄ negative electrode materials were prepared with polymer network gel method. The polymer network gel method has various effects on the structure, morphology and electrochemical properties of materials. Besides, the calcination temperature and calcination time were also the key factors to the electrochemical properties of the materials. In this paper, the effects of the ratio of monomer and crosslinker, calcination temperature and calcination time on ZnMoO₄ materials were studied by single variable method, the preparation process was optimized, and its characterization and electrochemical tests were carried out. After 100 cycles, the optimized ZnMoO₄ electrode has a discharge capacity of 374.0 mAh· g^?1, 332.5, 263.5 and 177.1 mAh · g^?1 at current densities of 0.1, 0.5, 1.0 and 2.0 A g^?1, respectively. The electrochemical results show that the optimized ZnMoO₄ has high capacity, large rate capability and excellent cycle stability.     

Carboxylated graphene oxide/polyvinyl chloride as solid-phase extraction sorbent combined with ion chromatography for the determination of sulfonamides in cosmetics

A carboxylated graphene oxide/polyvinyl chloride (CGO/PVC) material was prepared as a sorbent for the selective extraction of sulphonamides from complex sample. After being dispersed in buffer solution, sample was transferred into the prefabricated solid-phase extraction (SPE) column, which integrated extraction and cleanup into one single-step. A multi-response optimization based on the Box-Behnken design was used to optimize factors affecting extraction efficiency. Compared with the commonly commercial sorbents including MCX, WCX and C₁₈, CGO/PVC hybrid material had higher extraction selectivity and capacity to sulphonamides. The limits of detection and quantification for seven target compounds were in the range of 3.4–7.1 μg/L and 11.4–23.7 μg/L, respectively. The self-assembly SPE cartridge was successfully used to enrich seven analytes in anti-acne cosmetics prior to ion chromatography detection with good recoveries of 87.8–102.0% and relative standard deviations of 1.2–6.4%, implying that this method was suitable for routine analysis of cosmetics.     

New Monoterpenoids from Fruits of Gardenia jasminoides var. radicans

One new lactone, cyclopentanepyrone A ( 1 ), and two new monoterpenoids, gardeterpenone A ( 2 ) and jasminoside V ( 3 ), were isolated from the fruits of Gardenia jasminoides var. radicans, along with four known monoterpenoids, 4 – 7 , which were isolated from this plant for the first time. The structures of the isolates were elucidated by extensive spectroscopic studies, including UV, IR, 1D‐ and 2D‐NMR, ESI‐MS, HR‐ESI‐MS, and CD experiments.     

Silicification‐Induced Cell Aggregation for the Sustainable Production of H2 under Aerobic Conditions

Photobiological hydrogen production is of great importance because of its promise for generating clean renewable energy. In nature, green algae cannot produce hydrogen as a result of the extreme sensitivity of hydrogenase to oxygen. However, we find that silicification‐induced green algae aggregates can achieve sustainable photobiological hydrogen production even under natural aerobic conditions. The core–shell structure of the green algae aggregates creates a balance between photosynthetic electron generation and hydrogenase activity, thus allowing the production of hydrogen. This finding provides a viable pathway for the solar‐driven splitting of water into hydrogen and oxygen to develop green energy alternatives by using rationally designed cell–material complexes.     

藤黄酸重排反应产物研究

藤黄酸能显著抑制多种人类肿瘤细胞的增殖,在酸性环境中易发生重排反应,其重排产物对肿瘤细胞也具有很强的抑制作用.通过波谱技术确定了两个藤黄酸的重排反应产物的结构并归属了其波谱数据.细胞毒活性测试显示,两个重排产物对A549,HCT116和MDA-MB-231显示很强的抑制作用.